Theory of entanglements and tube confinement in rod-sphere nanocomposites

We formulate a microscopic theory for the polymer transverse confinement length and associated dynamic potential for a mixture of infinitely thin rods and hard spheres based solely on topological entanglements and excluded volume constraints. For fixed spheres, the needle effective tube diameter decreases with particle loading, and is largely controlled by a single dimensionless parameter involving all three key length-scales in the problem. A crossover from polymer entanglement to nanoparticle-controlled tube localization with increased loading is predicted. A preliminary extension to chain melts exhibits reasonable agreement with a recent simulation, and experimentally testable predictions are made. This work establishes a first-principles theoretical foundation to investigate a variety of dynamical problems in entangled polymer nanocomposites.